Method of controlling insects and acarina with cyanoalkylaldoxime carbamates

ABSTRACT

Insecticidal and acaricidal compounds are provided having the formula: WHEREIN: R1 and R2 are each selected from the group consisting of hydrogen, lower alkyl, and allyl, provided that when either R1 or R2 is hydrogen, the other substituent must be lower alkyl or allyl, and R3, R4, R5, R6, R7, and R8 are each selected from the group consisting of lower alkyl, hydrogen and phenyl, and N IS 0 OR 1. The above compounds are prepared by a variety of process routes from novel cyanoalkylaldoxime intermediates of the formula: WHEREIN R3,R4,R5,R6,R7, R8 and n are as defined above.

United States Patent Addor et al.

[ 51 Aug. 1, 1972 [54] METHOD OF CONTROLLING INSECTS AND ACARINA WITH CYANOALKYLALDOXIME CARBAMATES [72] Inventors: Roger Williams Addor; David Edgar Ailman, both of Pennington, NJ.

[73] Assignee: American Cyanamld Company,

Stamford, Conn.

[22] Filed: April 15, 1971 [2l] Appl. No.: 134,426

Related [1.8. Application Data [62] Division of Ser. No. 812,325, April 1, 1969,

Pat. No. 3,621,049.

[52] US. Cl ..424/327 5 1] Int. Cl. ..A0ln 9/20 [58] Field of Search ..424/327 Primary Examiner-Albert T. Meyers Assistant Examiner-Dale R. Ore Attorney-Robert P. Raymond 5 7 ABSTRACT insecticidal and acaricidal compounds are provided having the formula:

The above compounds are prepared by a variety of process routes from novel cyanoalkylaldoxime intermediates of the formula:

lilies, v \t/ i. t.

wherein R ,R ,R -,,R ,R R and n are as defined above.

4 Claims, No Drawings METHOD OF CONTROLLING INSECTS AND ACARIN A WITH CY ANOALKYLALDOXIME CARBAMA'I'ES This application is a divisional of application Ser. No. 812,325, filed Apr. 1, 1969, now US. Pat. No. 3,621,049.

SUMMARY OF THE INVENTION This invention relates to storage stable cyano'alltylaldoxime carbamates represented by the formula:

iiitirir wherein R R R,, R,,, R R and n are as defined above. These compounds (II) are useful as intermediates in preparing the insecticidal and acaricidal cyanoalkylaldoxirne carbamates (I) described above.

The term "lower alkyl" means straight and branched chain alkyl radicals containing from one to three carbon atoms; illustrative members are methyl, ethyl, npropyl, and isopropyl.

PRIOR ART The following references represent the closest prior art known to applicants:

1. U. S. Pat. No. 3,217,037

2. U. 8. Pat. No. 3,400,153

3. "The synthesis and Insecticidal Properties of Some Cholinergic Trisubstituted Acetaldehyde O- (Methyl-carbamoyl)oximes," Payne et al., J. Agr. Food Chem, Vol. l4, No. 4, July-August, 1966, pgs. 356-365.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Compounds The following compounds are illustrative of the cyanoalkylaldoxime carbamates of this invention reference to compound I xxxx xxxxgv :r.:1:xx2

l I I I? I I I I? caci-t ca. 11 (:11. ca, 11 11 o l-c i, 11 g". 2 on. :1 g 511. 11 11 ila 0 ca. 11 11 11 cu. 0 on. on. 11. 11 11 11 0 e11. 11 11 11 11 e11, e11, 1 c, 11 gm 11 11 ca. 11 1 11 551, 11 11 11 ca. 11 1 011. CH. an. 011. 11 11 11 1 on. 11 cu 11 11 11 1-1 1 on. 11 11 c,11. 11 1 011. C11. 11 11 cal. 11 1 11-c.11, "-0.11, 11 011. 1:11. 11 11 1 Certain cyanoalkylaldoxime carbamates of this invention are characterized by a high degree of stability during prolonged storage. For example, the compounds have shown substantially no decomposition after storage intervals of at least 3 months at ambient conditions of temperature and humidity.

The followin are illustrative of the cyanoalltylaldoximes of this invention reference to compound ll ocesses The cyanoalkylaldoxime carbamates (I) of this invention wherein R and R, are not both lower alkyl or allyl are readily prepared by reacting a novel cyanoalkylaldoxime of the formula:

\lJ. it. it.

with hydroxylamine wherein R R R R R R and n are as defined above in the presence of an inert solvent and about one mole of a base such as sodium acetate, pyridine, sodium bicarbonate, or calcium carbonate.

The required cyanoalkylaldehydes (III) are either readily available or can be readily prepared from known starting materials in accordance with procedureslmowntothoseskilledintheatt'lhe preparation of a typical cyanoalkylaldehyde Ill is exemplified in Example A hereinbelow.

The compounds of this invention wherein R, and R, are both lower alkyl or allyl are conveniently prepared by either of two processes. in the first process, the cyanoalkylaldoxime ll shown above is reacted with a di-substituted carbarnoyl chloride of the formula:

in the presence of about 1 mole of a base such as potassium-t-butoxide or sodium methoxide wherein R and R, are as previously defined.

In the second process, the cyanoalkylaldoxime (ll) shown above is reacted first with phosgene IV in the presence of an inert solvent and about one mole of a base such as 2,6-lutidine or potassium t-butoxide to produce an intermediate chlorocarbonate (V) in accordance with the following equation:

n l 4 I Suitable inert reaction solvents for carrying out the above reactions include benzene, toluene, ethylene chloride, acetone, and t-butanol.

Reaction temperatures may range from to 75 C. with a range of 50 C. preferred. The reactions may be run under superatmospheric, atmospheric, or

sub-atmospheric pressure with atmospheric pressures preferred.

UTILITY The cyanoalkylcarbamates of this invention are useful for controlling a variety of insects and acarina such as those shown in Examples 22,23, and 24 hereinbelow. The compounds are particularly eflective against aphids and mites. These two pest species are often found in the same environment but are known to be difficult to control with a single chemical since the mites,

4 in particular, build up a resistance to phosphorus-containing insecticides. The inventive compounds are also most efl'ective against ticks.

They are highly efiective when applied to domestic anirmls such as cattle, pigs, and sheep which are infested with insects or acarina, and particularly when applied to animals infested with arthropods such as ticks, by the use of dipping vats, sprays, spray-races, dusts, and other methods known to those skilled in the art.

They may be applied to the foliage of plants as dusts or liquid sprays to protect them from insects and mites which feed thereon; they may also be incorporated in or applied to the soil in order to protect germinating and growing plants from soil-borne pests which attack the root systems and stems of said plants; or they may be applied to the breeding sites of pests to control both the larvae and adult stages of breeding pest populations. In the latter situations the compounds may be applied in conventional formulations such as dust, dust concentrates, granular materials, wettable powders, emulsifiable concentrates and the like. They may be employed as an emulsion in water or other non-solvents to which suitable surfactants, wetting agents or emulsifying agents have been added. They may be applied on solid carriers, such as tales and clays, as for example kaolin clay or fuller's earth, or on such carriers as chalk, wood flour, silica, charcoal, activated carbon or other inert powders. AS a wettable powder, the compounds of this invention may be applied to easily wettable carrier materials, such as attaclay, with or without the aid of surfactants, or on less readily wettable carriers in combination with suitable surfactants.

Advantageously, the compounds of the invention may also be applied by the most modern techniques of low volume or ultra-low volume application wherein the compound is applied essentially as a technical material or in combination with a minor amount of hydrocarbon solvent such as Panasol AN-S, Socal 44-1. or Esso HAN (all commercially available).

The compounds of this invention may also be applied in combination with other essentially technical materials, such as malathion, which in addition to having insecticidal properties also serve as a formulation vehicle.

The cyanoalkylaldoximes derive their utility as intermediates in the preparation of the useful cyanoalkylaldoxime carbamates. This utility is amply shown in Examples l0 through 21 hereinbelow.

The following examples are provided to further illustrate the invention.

EXAMPLE A (PRIOR ART) Preparation of 2,2-Dimethyl-4-cyanopentanal A stirred mixture of 7.2 g. of isobutyraldehyde, 6.7 g. of a-methylacrylonitrile, and 10.0 g. of a basic ion exchange resin (Rexyn CGL in the OH form) was heated at about C. for 6 hours. The mixture was then cooled, filtered, and concentrated under vacuum.

3,681,505 6 Distillation of the residue afforded 4.8 g. of the color- EXAMPLE 4 less roduct, b. 7o-73 c./o.1s mm, 11 =1.4344.

115a. Calcd for 0,11,,10; c, 69. 1; 113.4; N, 10.1. l Found: c, 68.4; H, 9.6; N, 9.5.

5 EXAMPLE 1 Preparation of 2,2-dimethyl-4-cyanobutyraldoxime Z Nc-cH1cI1,o-crr=N0u NC omen, -cH:No1-1 H Following the procedure used to prepare 2,2-

A solution of 32 sof hydroxylamme hydrochlonde 1s dimethyl-4-cyanobutyraldoidme( i.e., Example 1 but in 45 ml. of water was added to a solution containing replacing 2,2.dimethy|4 yambutym1dehyde n, 2. 8- of ziz'dlmelhykb m y a g -P- methyl-2-phenyl-4-cyanobutyraldehyde gave, from 8 -8 C- 0 and 36 sof Py In 450 1111- 45.0 g. of the aldehyde, 42.3 g. ofthe oxime as a pink of alcohol gave a mildly exothermic reaction. The solui], tion wa warme to 45 C- to mp t h reac i n. Anal. Calcd. for c n mo c, 71.26; H, 6.98 N, concentrated to remove alcohol, diluted with water and 13.85. the oxime isolated by extraction with benzene, washing Found: C, 70.8; H, 6.8; N, 13.4. and evaporation. The oxime 37.0 g. was obtained as a straw colored oil which solidified at room tempera- EXAMPLE 5 ture. Analysis, calculated for 0,11,,N,0 19.99 percent P arati of 2,2-Diethyl-3-cyanobutyraldoxirne N; Found 20.17% N.

EXAMPLEZ NcoH-c-cH=Non Preparation of 2,2-D1methyl-4-cyanopentanaloxune E Thebo OdCt edfll' bst z a ve pr u was prepar o owing su an- NC 21101114; 011 tially the same procedure as in Example 1 except that the 2,2-dimethyl-4-cyanobutyraldehyde was replaced with 2,2-diethyl-3-cyanobutyraldehyde.

Following the same procedure used to prepare 2,2- EXAMPLE 6 dimethyl-4-cyanobutyraldoxime i.e., Example 1 but replacing 2,2-dimethyl- 40 Preparation of 2,3,3-trimethyl-4-cyanopentanaloxime 4-cyanobutyraldehyde with 2,2-

dimeIhyIA-cyanopentanal as prepared in Example A gave a CH; CH; CH1

60 percent yield of crude N C J; H H C 2N o H product, m.p. 3346 C. A '1:

sample, recrystallized from H:

chloroform-petroleum ether at about 60 C., ave colorless crymla. m-p-l: -0-39.0' c. The above product was prepared following substan- Anal. Calc d. for C H N,O: C, 62.4; H, 9.1; N, 18.2. n the same procedure as in Example 1 except that Found: 61-35 the 2,2-dimethyl-4-cyanobutyraldehyde was replaced EXAMPLE 3 by 2-methyl-3,3-d1methyl-4-cyanopentanal Preparation of 2-Ethyl-2-methyl-4-cyanobutyraldox- EXAMPLE 7 ime Preparation of 2,2dimethyl-4-cyano-4-phenylbutyraldoxime -phenylbutyraldoxime 0,11, NC-CHz-CIh-llF-Cfl -NOH Following the same procedure used to prepare 2,2 50 dirnethyl-4cyanobutyraldoxime i.e., Example 1 but I replacing 2,2-dimethyl-4-cyanobutyraldehyde with 2- ethyl-2-methyl-4-cyanobutyraldehyde gave an 85.7 percent yield of product melting below room tempera- 65 The above product was prepared following substanture. tially the same procedure as in Example 1 except that Anal. Calc'd. for C,,H N,O:C, 62.3; H, 9.2; N, 18.2 the 2,2-dimethyl-4-cyanobutyraldehyde was replaced Found: C, 6| .5; H, 9.3; N, 17.8 with 2,2-dimethyl-4-cyano-4phenylbutyraldehyde.

EXAMPLE 8 Preparation of 3Cyanopropionaldoxime NCCl-I,CH,Cl-l NOH The above product was prepared following substantially the same procedure as in Example l except that the 2,2-dimethyl-4-cyanobutyraldehyde was replaced with 3-cyanopropionaldehyde.

EXAMPLE 9 Preparation of 2-Ethyl-3-cyanobutyraldehyde C H; I 8. Q :515: LHENQIL The above product was prepared following substantially the same procedure as in Example 1 except that the 2,2-dimethyl4-cyanobutyraldehyde was replaced with 2ethyl-3-cyanobutyraldehyde.

EXAMPLE Preparation of 2,2-Dimethyl-4-cyanobutyraldoxime-N- methylcarbamate To a stirred mixture of 37.0 g. of 2,2-dimethyl-4- cyanobutyraldoxime in 175 ml. of benzene was added to 17.5 g. of methyl isocyanate followed by 0.2 ml. of triethylamine. A very mildly exothermic reaction occurred. Infrared absorption spectra indicated reaction was complete in 3.5 hours at room temperature. After partial concentration of the mixture under vacuum to remove any unreacted methyl isocyanate, it was diluted with benzene and ether, washed with water and with saturated salt solution and dried with magnesium sulfate. The carbamate was recovered by evaporation of solvent and crystallized from ether to obtain 42 g. of white solid, mp. 42.543 C.

Anal. Calcd. for C,H ,N O,: 21.31% N Foundi 21.09% N EXAMPLE ll Preparation of 2,2-Dimethyl-4-cyanobutyraldoxime- N,N-dimethylcarbamate on, 0 on, i i NC 011,011, I CH=NO N\ EXAMPLE 12 Preparation of 2,2-Dimethyl-4-cyanobutyraldoxime-N- ethylcarbamate The procedure was the same as that used for preparing the N-methylcarbamoyl derivatives (i.e., Example l0) except ethyl isocyanate replaced methyl isocyanate. The product was obtained as a pale tan oil in 73 percent yield.

Anal. Calcd. for C, ,H, N,O,: C, 56.85; H, 8.11; N,

19.89. Found: C, 57.76; H, 8.70; N, l9.6l'.

EXAMPLE 13 Preparation of 2,2-Dimethyl-4-cyanobutyraldoxime-N- allylcarbamate The procedure was the same as that used for preparing the N-methylcarbarnoyl derivative (i.e., Example 10) except that allyl isocyanate replaced methyl isocyanate. The product was obtained in 89 percent yield as a yellow oil.

Anal. Calcd. for c,.H,,N,o,= C, 59.17; H, 7.68; N,

18.82. Found: C, 59.91; H, 8.23; N, 19.60.

EXAMPLE 14 Preparation of 2,2-Dimethyl-4-cyanopentanaloxime-N- methylcarbamate The procedure was that used to prepare 2,2- dimethyl-4-cyanobutyraldoxime-N-methylcarbamate (i.e., Example 10) except that 2,2-dimethyl-4- cyanopentanaldoxime (as prepared in Example 2) replaced 2,2-dimethyl-4-cyanobutyraldoxime. The yield of crude oily product was percent. Further purification was effected by chromatography using a magnesium silicate column and eluting first with methylene chloride and then with ether.

. 2 h! AnlaglgCalcd. for C,,H N,0,: C, 56.9; H, 8.1; N, tyraldoxime and methyl(allyl)carbamoyl chloride replacedthedimeth carbamogrlchloride'lhe uct Found: C, 56.5;1-1, 8.2; N, 18.8. was isolated as an oil prod EXAMPLE l 5 EXAMPLE 18 Preparation of 2-Ethyl-2-methyl4cyanobutyraldox- Preparation of2,3,3-Trimethyl4-cyanopentanaloximeime-N-methylcarbamate N,N-di-isopropylcarbamate Call! 0 CH; CH; CH; 0 Cflh-i NCCHzClh-l-CH=N0PJNHCH: NchH- H-cH=No-t :-N

CH; Hg 0 1-1 The Procedure was mat w P p is The procedure was that used to prepare 2,2-

dimethylAcyanobutyraldoxime-N-Mthylcarbamate dimm lmmbut mldmdmlq lqdmeth k rb Emple x ep that 2-ethyl-2-methyl-4- mate (i.e. Example 11) except that 2,3,3-trimethyl-4- cyanobuyyraldomme replaced q y -q cyanopentaldoxime replaced 2,2-dimethyl-4-cyanobuty x The oflyyroduct, obtained In P tyraldoxirne and di-isopropylcarbamoyl chloride yield, showed y y wntafnimfion y thin layer replaced the dimethylcarbamoyl chloride. The oily chromatography on 811m gel s lvewent methanol product has the expected carbonyl absorption at about in chloroform for developing and iodine vapor for de- 1,710 -L tection of spots.

Anal. Calcd. for c,.,H,,N,o,; C, 56.9; 1-1, 8.1; N, EXAMPLE 19 Preparation of 2,2-Dimethyl-4-cyano-4-phenylbutyral- Found. C, 57.8, H, 8.5,N, 19.1. do Net-Mead m EXAMPLE 16 ime-N-methylcarbamate I Nr: uu-c1r-, -o1r=N-0- l-Nncn 3 The procedure was the same as that for the preparation of 2,Z-dimethylLcyanobutyraldoxime-N-methyl- 40 carbamate (i.e., Example 10) except that 2,2-dimethyl- 4-cyano-4-phenylbutyraldoxime replaced 2,2- The procedure was that used to prepare 2,2- dimethyl-4-cyanobutyraldoxime-N-methylcarbamate dlmlethyl ffi m "{1 (i.e. Example 10) except that 2-methyl-2-phenyl-4- f r g .g e o y pr cyanobut raldoxime replaced 2,2-dimethy-4-cyanobua tyraldoxime. :rhe crude plrlrfiuct from 35.0 g. 3f the EXAMPLE 20 oxime was c omatograp on magnesium s' icate eluting with carbon tetrachloride and then with Preparation of 3-Cyanoaldoxrme-N-methylcarbamate methyl :ne chloride to give 28.9 g. of pure carbamate as aviscc us oil. E

An: I. Calcd. for C H MQ: C, 64.84; H, 6.61; N, NQTCHCHFFIHQ-TQ'T 'Mlcm 6.2L Fc And: C, 65.4; H, 6.8; N, 15.8. 3-Cyanopropionaldoxime was reacted with methyl isocyanate in the same way as was 2,2-dimethyl-4- EXAMPLE 17 cyanobutyraldoxime of Example 10. The product, a pal-mien f 2 2 3 m low melting solid, shows 3116 expected nitrile absorption N -l-methyl(allyl)carbamate bandalabout 2250a EXAMPLE 21 on, em, 0 CH, l/ Preparation of Z-Ethyl-3-cyanobutyraldox1me-N,N- I m methyKaIIyD-carbarnate um, umcuzcu-l The procedure was that used to prepare 2,2- dimethyl-4-cyanobutyraldoxime-N,N-dimethylcarbamate (Le. Example 11) except that 2,2-diethyl-3- N cyanobutyraldoxime replaced 2,2-dimethyl-4-cyanobucm,

The procedure was that used to dimethyl-4-cyanobutyraldoxime-NN-dirnethylcarbamate (Example ll) except that 2-ethyl-3-cyanobutyraldoxime replaced 2,2-dimethyl-4-cyanobutyraldoxime and methyl(ethyl) carbamoyl chloride replaced dimethylcarbamoyl) chloride. The product, an oil, shows typical carbamate carbonyl absorption at about 1,700 m EXAMPLE 22 Efficacy Against Mites and Aphids The eflicacy of the inventive cyanoalkylaldoxime carbamates against mites and aphids was demonstrated in accordance with the following test procedures.

1. Bean aphid Aphirfabae Scopoli Compounds are tested as solutions in 65 percent acetone-35 percent water. Two-inch fiber pots, each containing a nasturtium plant 2 inches high and infested with about 150 aphids 2 days earlier, are placed on a turntable (4rprn) and sprayed for two revolutions with a No. 154 DeVilbiss Atomizer at 20 psi air pressure. The spray tip is held about 6 inches from the plants and the spray is directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays. Mortality counts are made after holding for one day at 70 F., and 50% r.h.

LC-SO values are obtained in the standard manner by plotting percent mortality as a function of the compound concentration for a variety of concentrations. The term LC-SO means the compound concentration expressed in ppm required to kill 50 percent of the aphids.

2. Two-spotted spider mite Tetranychus urticae (Koch) Sieva lima bean plants with primary leaves three to four inches long are infested with about 100 adult mites per leaf four hours before use in this test. The mite and egg infested plants are dipped for three seconds in the solutions used in the above test, and the plants set in the hood to dry. They are held for two days at 80 F.,

prepare 2,2-

60% r.h., and the adult mite mortality counted on one leaf under a t c microscope. The other leaf is left on the plant an additional five days and then examined at 10X powertoestimate the kill ofeggs andof newly-hatched nymphs, giving a measure of ovicidal and residual action, respectively.

Since mites are known to develop resistance to phosphorus containing insecticides, the were also tested agains a strain of phosphate resistant" mites as described below. 3. "Phosphate-Resistant" Mites The phosphate-resistant colony of two-spotted spider mites (Tetranychur um'cae [Koch] used were subjected to repeated treatments with a lzlzl mixture of dirnethoate, malathion and parathion periodically over aperiodofQyears. LD testsshowedth'mcolonytobe approximately 50 times more resistant to these chemicals than the susceptible colony. The inventive compounds were tested against these phosphate-resistant mites following the same procedure used for the susceptible mites.

Mite LC-SO values were determined in the manner described above or aphid LC-SO values. 4. Mite Systemic Tests The compoundtobe tested is formulated as anemulsion containing 0.l gram oftest material, 0.2 grams of Alrodyne 315 emulsifier, 10 ml. of acetone and ml. of water. This is diluted ten-fold with water to give a ppm emulsion for the test. A sieva lima bean plant with only the primary leaves unfolded is cut ofi just above soil level and inserted into a two ounce bottle of 100 ppm emulsion and held in place by a bit of cotton wrapped around the stem. The bottle is then placed in a ventilated box with the leaves extending outside the box, such that any possible fumes from the compound will bedrawn out the end ofthe box rather than rising to aflect the test leaves. About 50 adult two-spotted spider mites are placed on each leaf. After holding three days at 80 F. and 60% r.h., mortality estimates are made.

Results are presented in Tablel.

The high activity against aphids and mites is apparent from the data of Table I. The compounds also have systemic activity against mites.

It should be noted that although the compounds of this invention exhibit activity against aphids ble to well known insecticides such as parathion and dimethoate, they show greater activity than these two materials against susceptible mites (1.5 to 2 times greater) and remarkably greater activity (150 to 300 times)thanthesetwocompoundsagainstastrainof phosphate resistant mites. Since mites and aphids are often found in the same environment, the activity against phosphate resistant mites is of particular importance since it permits control of aphids and phosphate-resistant mites by application of a single chemical.

EXAMPLE 23 Eflicacy Against Insects The efficacy of the inventive cyanoalkylaldoxime carbamates against insects was demonstrated in accordance with the following test procedures. 1. Large milkweed bug-Oncopeltusfasciatus Dallas compounds are formulated as 1 percent dusts by mixing 0.1 gram of the compound with 9.9 grarm of Pyrax ABB talc, wetting with 5 ml. of acetone and grinding with a mortar and pestle until dry. 25 mg. of

the l percent dust is sprinkled evenly over the glass bottom of a 7-inch diameter cage, using a screen-bottom plastic cup about five-eighths inch in diameter as an applicator, giving a deposit of approximately mglsq. ft. (0.108 mgJsq. cm.) of the lpercent dust. Water is supplied in a 2-ounce bottle with a cotton wick, twenty adultbugsareaddedandascreencoverplacedonthe top. Mortality counts are made alter holding for three days at 80 F. and 60% r.h. 2. l-iousefly-Musca domestica Linnaeus Groups of 25 adult female houseflies are lightly anesthetized with C0,, placed in wide-mouthed pint" masonjars,andcoveredwithascreencap.'l'hetest compound is formulated as an emulsion containing 0.1 gramoftest material, 0.2 gramofAlrodyne 315 emulsifier, 10 ml. of acetone and 90 ml. of water. Two milliliters of ms emulsion are diluted to 40 ml. with 10 percent sugar solution in a lO-gram glass vial, giving a concentration of 50 ppm. The mouth of the vial is covered with a single layer of cheesecloth, inverted and 'placedonthescreencap,sothatthefliescanfeedon the solution through the screen. Mortality counts are made afterZdaysat 80 F.

The compound of Examples l0, l2, l3, l4, and

killed 100 percent of the milkweed bugs while the coml0 testgroupcontainedabout l0ormorenymphs(see% kill) of a single species and all tests were replicated. TheresultsareshownbelowinTablell.

TABLEll Compound Prepared in Example Number 20 PPM 10 100 ll 80 l4 9] i5 20 We claim:

LArnethodforcontrollinginsectsandacarina whichcornprisesapplyingtosaidinsectsandacarinaan insecticidally and acaricidally elfective amount of at least one ofthe compoundsofthe formula.

wherein:

R, and R are each selected from the group consistingoflrydrogen, lower alkyl ofC, to C,, and allyl, providedthat when either R, or R, is hydrogen, the fir substituent mustbe lower alkyl ofC. to C or 11., R R R R and R. are each selected from the groupconsistingofloweralkylofQtoQ, hydrogen,andphenyl,and

hisOor l.

2. A method for protecting vegetation from destructionbyinsectsandacarinawhichapplyingto said vegetation an insecticidally and acaricidally efi'ectiveamoimtofatleastoneofthecompoundsofclaim terior of said anirmls an imecticidally and acaricidally efiective amount of at least one compound of claim 1. 

2. A method for protecting vegetation from destruction by insects and acarina which comprises applying to said vegetation an insecticidally and acaricidally effective amount of at least one of the compounds of claim
 1. 3. The method of claim 1 wherein said insects are aphids and said acarina are ticks and mites.
 4. A method for controlling insects and acarina on domestic animals which comprises applying to the exterior of said animals an insecticidally and acaricidally effective amount of at least one compound of claim
 1. 